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1 Electrnic Supplementary Material (ESI) fr Jurnal f Materials Chemistry A. This jurnal is The Ryal Sciety f Chemistry 2015 Supprting Infrmatin Ratinal Design and Synthesis f Plythiureas as Capacitr Dielectrics Rui Ma, Vinit Sharma, Aarn F. Baldwin, Mattews Tefferi, Id Offenbach, Mukerrem Cakmak, Yang Ca, Rampi Ramprasad, Gregry A. Stzing* *Crrespndence t: stzing@mail.ims.ucnn.edu

2 Synthesis and Chemical Structure Determinatin PDTA-ODA: T a dry 50ml 3-neck flask, 0.961g (5mml) f para-phenylene diisthicyanate 1.001g (5mml) 4,4'-xydianiline and 20ml NMP were added under inert atmsphere with stirring. After 6h at rm temperature, the reactin mixture was pured int methanl with fibrelike precipitatin, fllwed by washing with methanl and dried at 50 C in vacu vernight. White precipitate was btained in 91% yield (1.78g). FTIR: ν max /cm (N-H st), 3030 (ar C- H st), 1510 (ar C-C), 1340 (C-N st), 1240 (C=S st), 1160 and 1010 (ar C-O-C st). 1 H NMR δ H (500 MHz; DMSO-d 6 ) 6.99 (4 H, d, benzene), 7.43 (4 H, s, benzene), 7.46 (4 H, d, benzene) and 9.72 (4 H, s, NH). Chain end: 4.98 ( H, s, NH 2 ), M n =21537 g/ml. PDTC-MDA: The preparatin is similar t that f PDTC-ODA, with 0.961g (5mml) f paraphenylene diisthicyanate and 0.991g (5mml) f 4,4'-diphenylmethanediamine. White fibrelike slid was btained in 94 % yield (1.84g). FTIR: ν max /cm (N-H st), 3020 (ar C-H st), 1510 (ar C-C), 1300 (C-N st), 1250 (C=S st). 1 H NMR δ H (500 MHz; DMSO-d 6 ) 3.88 (2 H, s, CH 2 ), 7.20 (4 H, d, benzene), 7.37 (4 H, s, benzene), 7.41 (4 H, d, benzene) and 9.71 (4 H, s, NH). Chain end: 5.24 ( H, s, NH 2 ), M n =56360 g/ml. PDTC-PhDA: The preparatin is similar t that f PDTC-ODA, with 0.961g (5mml) f paraphenylene diisthicyanate and 0.991g (5mml) f 4,4'-diphenylmethanediamine. White fibrelike slid was btained in 94 % yield (1.84g). FTIR: ν max /cm (N-H st), 3020 (ar C-H st), 1510 (ar C-C), 1310 (C-N st), 1250 (C=S st). PDTC-HDA: The preparatin is similar t that f PDTC-ODA, with 0.961g (5mml) f paraphenylene diisthicyanate and 0.581g (5mml) f 1,6-diaminhexane. White fibre-like slid was btained in 93 % yield (1.43g). FTIR: ν max /cm (N-H st), 3020 (ar C-H st), 2930 (C-H st), 1510 (ar C-C), 1310 (C-N st), 1230 (C=S st). 1 H NMR δ H (500 MHz; DMSO-d 6 ) 1.32 (4 H, m, CH 2 ), 1.54 (4 H, m, CH 2 ), 3.45 (4 H, m, CH 2 ), 7.33 (4 H, s, benzene), 7.65 (2 H, s, NH), and 9.39 (2 H, s, NH). Chain end: 1.96 ( H, s, NH 2 ), M n = g/ml. PDTC-HK511: The preparatin is similar t that f PDTC-ODA, with 0.961g (5mml) f paraphenylene diisthicyanate and 1.10g (5mml) f Jeffamine HK511. White fibre-like slid was btained in 87 % yield (1.80g). FTIR: ν max /cm (N-H st), 3040 (ar C-H st), 2973 (C-H st), 1510 (ar C-C), 1310 (C-N st), 1230 (C=S st), 1103 and 1038 (ar C-O-C st). 1 H NMR δ H (500 MHz; DMSO-d 6 ) (7 H, m, Me), (12 H, m, CH 2 ), 4.49 (2 H, m, CH), 7.36 (4 H, s, benzene), 7.52 (2 H, s, NH), and 9.44 (2 H, s, NH). Chain end: 1.27 ( H, s, NH 2 ), M n = g/ml. Thiphsgene-MDA: T a cmpletely dried fur neck flask equipped with drpping funnel, distillatin and a safety trap, 3.96g 4,4'-diphenylmethanediamine and 2.26g 1,4-diazabicycl [2.2.2]ctane (DABCO) were well mixed then cled with ice bath. 2.30g thiphsgene was

3 carefully and slwly added t the mixture thrugh drpping funnel at 0 C. The reactin was then carried ut at rm temperature fr 24h. Deinized water and methanl was used fr precipitatin and washing, fllwed by drying 50 C in vacu. Light yellw fibre like plymer was btained after purificatin in 85% yield (4.10g). FTIR: ν max /cm (N-H st), 3020 (ar C- H st), 1510 (ar C-C), 1320 (C-N st), 1250 (C=S st). 1 H NMR δ H (500 MHz; DMSO-d 6 ) 3.86 (2 H, s, CH 2 ), 7.18 (4 H, d, benzene), 7.35 (4 H, d, NH), and 9.67 (2 H, s, NH). Chain end: 6.93 ( H, m, tw benzene), M n =44615 g/ml. Thin Film Prcessing PDTC-ODA: A 10wt% DMSO slutin was used fr casting large scale film n a brsilicate glass substrate by Dr. Blade Film Applicatr. The blade gap was 254μm. Films were casted at 80 C fllwed by drying n the ht plate at 100 C fr 6h. After peeling ff the glass, films were dried under vacuum at 120 C vernight. The film thickness is 13-14μm. PDTC-MDA: A 10wt% DMAc slutin was used fr casting large scale film n a brsilicate glass substrate by Dr. Blade Film Applicatr. The blade gap was 254μm. Films were casted at 60 C fllwed by drying n the ht plate at 80 C fr 6h. After peeling ff the glass, films were dried under vacuum at 100 C vernight. The film thickness is 13-14μm. PDTC-HDA: A 10wt% DMAc slutin was used fr casting large scale film n a brsilicate glass substrate by Dr. Blade Film Applicatr. The blade gap was 500μm. Films were casted at 60 C fllwed by drying n the ht plate at 80 C fr 6h. After peeling ff the glass, films were dried under vacuum at 100 C vernight. The film thickness is 9-10μm. PDTC-HK511: A 15wt% DMAc slutin was used fr casting large scale film n a brsilicate glass substrate by Dr. Blade Film Applicatr. The blade gap was 500μm. Films were casted at 70 C fllwed by drying n the ht plate at 75 C fr 6h. After peeling ff the glass, films were dried under vacuum at 100 C vernight. The film thickness is 12-14μm. Thiphsgene-MDA: A 15wt% DMSO slutin was used fr casting large scale film n a brsilicate glass substrate by Dr. Blade Film Applicatr. The blade gap was 254μm. Films were casted at 80 C fllwed by drying n the ht plate at 100 C fr 6h. After peeling ff the glass, films were dried under vacuum at 100 C vernight. The film thickness is 11-13μm.

4 Time Dmain Dielectric Spectrscpy PDTC-ODA: PDTC-MDA: PDTC-PhDA: PDTC-HDA: PDTC-HK511: Thiphsgene-MDA: DC Breakdwn Field Weibull Distributin

5 Thiphsgen 1.74 (546 nm 1.72 (632 nm Refractive Index Measurement 546 (Green light) 632 (Red light) PDTC-ODA PDTC-MDA PDTC-HK PDTC-HDA D-E Hysteresis Lp:

6 PDTC-HDA: PDTC-MDA: PDTC-ODA:

7 PDTC-HK511: Thiphsgene-MDA: